Predictors of urinary levels of 2,4-dichlorophenoxyacetic acid, 3,5,6-trichloro-2-pyridinol, 3-phenoxybenzoic acid, and pentachlorophenol in 121 adults in Ohio.

Limited data exist on the driving factors that influence the non-occupational exposures of adults to pesticides using urinary biomonitoring. In this work, the objectives were to quantify the urinary levels of 2,4-dichlorophenoxyacetic acid (2,4-D), 3,5,6-trichloro-2-pyridinol (TCP), 3-phenoxybenzoic acid (3-PBA), and pentachlorophenol (PCP) in 121 adults over a 48-h monitoring period and to examine the associations between selected sociodemographic and lifestyle factors and urinary levels of each pesticide biomarker. Adults, ages 20-49 years old, were recruited from six counties in Ohio (OH) in 2001. The participants collected 4-6 spot urine samples and completed questionnaires and diaries at home over a 48-h monitoring period. Urine samples were analyzed for 2,4-D, TCP, 3-PBA, and PCP by gas chromatography/mass spectrometry. Multiple regression modeling was used to determine the impact of selected sociodemographic and lifestyle factors on the log-transformed (ln) levels of each pesticide biomarker in adults. The pesticide biomarkers were detected in ≥ 89% of the urine samples, except for 3-PBA (66%). Median urinary levels of 2,4-D, TCP, 3-PBA, and PCP were 0.7, 3.4, 0.3, and 0.5 ng/mL, respectively. Results showed that 48-h sweet/salty snack consumption, 48-h time spend outside at home, and ln(creatinine) levels were significant predictors (p < 0.05), and race was a marginally significant predictor (p = 0.093) of the adults' ln(urinary 2,4-D) concentrations. Strong predictors (p < 0.05) of the adults' ln(urinary TCP) concentrations were urbanicity, employment status, sampling season, and ln(creatinine) levels. For 3-PBA, sampling season, pet ownership and removal of shoes before entering the home were significant predictors (p < 0.05) of the adults' ln(urinary 3-PBA) levels. Finally for PCP, removal of shoes before entering the home and ln(creatinine) levels were significant predictors (p < 0.05), and pet ownership was a marginally significant predictor (p = 0.056) of the adults' ln(urinary PCP) concentrations. In conclusion, specific sociodemographic and lifestyle factors were identified that increased the exposures of these adults to several different pesticides in their daily environments.

Short-term variability and predictors of urinary pentachlorophenol levels in Ohio preschool children.

Pentachlorophenol (PCP) is a persistent and ubiquitous environmental contaminant. No published data exist on the temporal variability or important predictors of urinary PCP concentrations in young children. In this further analysis of study data, we have examined the associations between selected sociodemographic or lifestyle factors and urinary PCP concentrations in 115 preschool children over a 48-h period and assessed the 48-hour variability of urinary PCP levels in a subset of 15 children. Monitoring was performed at 115 homes and 16 daycares in Ohio (USA) in 2001. Questionnaires/diaries and spot urine samples were collected from each child. The median urinary PCP level was 0.8 ng/mL (range < 0.2-23.8 ng/mL). The intraclass correlation coefficient for urinary PCP was 0.42, which indicates fairly low reliability for a single sample over a 48-h period. In a multiple regression model, age of home and ln(creatinine levels) were significant predictors and sampling season, time spent outside, and pet ownership were marginally significant predictors of ln(urinary PCP levels), collectively explaining 29% of the variability of PCP in urine. To adequately assess short-term exposures of children to PCP, several spot urine measurements are likely needed as well as information regarding residence age, seasonality, time spent outdoors, and pet ownership.

Association of exposure to phenols and idiopathic male infertility.

Widespread human exposure to phenols has been documented recently, and some phenols which are potential endocrine disruptors have demonstrated adverse effects on male reproduction in animal and in vitro studies. However, implications about exposure to phenols and male infertility are scarce in humans. Case-control study of 877 idiopathic infertile men and 713 fertile controls was conducted. Urinary levels of bisphenol A, benzophenone-3, pentachlorophenol, triclosan, 4-tert-octylphenol (4-t-OP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP) and semen parameters were measured. After multivariate adjustment, we found 4-t-OP, 4-n-OP and 4-n-NP exposure was associated with idiopathic male infertility (p-value for trend: <0.0001, 0.014 and 0.001, respectively). Aside from these associations, 4-t-OP and 4-n-NP exposure was also associated with idiopathic male infertility with abnormal semen parameters. Moreover, we observed significant associations between sum alkylphenols (APs) exposure and idiopathic male infertility. There were no relationships between exposure to other phenols and idiopathic male infertility in the present study. Our study provides the first evidence that exposure to APs (4-t-OP, 4-n-OP and 4-n-NP) is associated with idiopathic male infertility.

Determination of nine environmental phenols in urine by ultra-high-performance liquid chromatography-tandem mass spectrometry.

A method was developed to determine nine environmental phenols, including bisphenol A, 2,3,4-trichlorophenol, 2,4,5-trichlorophenol, pentachlorophenol, triclosan (2,4,4'-trichloro-2'-hydroxyphenylether), 4-tert-octylphenol, 4-n-octylphenol, 4-n-nolyphenol and benzophenone-3 (2-hydroxy-4-methoxybenzophenone) in human urine using ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS-MS). The analytes were extracted and preconcentrated with solid-phase extraction, and then quantified with UPLC-electrospray ionization (negative ion mode)-MS-MS using multiple reaction monitoring mode. Limits of detection of the nine phenols ranged from 0.02 to 0.90 ng/mL. This method was further validated by the determination of phenols in 325 human urine samples that generated data regarding the exposure of various phenols to Chinese adults without occupational exposure to phenols.

Global trends and diversity in pentachlorophenol levels in the environment and in humans: a meta-analysis.

Pentachlorophenol (PCP) was banned or restricted in many countries worldwide because of its adverse effects on the ecological environment and humans. However, the endocrine disrupting effects caused by low environmental PCP exposure levels has warranted more analysis. We reviewed 80 studies conducted in 21 countries and published between 1967 and 2010, using meta-regression analysis to examine the time trends and regional differences in PCP levels. The results suggested that in indoor air, bodies of water, freshwater sediments in western countries, invertebrates and freshwater vertebrates, PCP levels had declined over time, with half-lives ranging from 2.0 years to 11.1 years. However, in marine sediments/vertebrates and Chinese surface water/sediments, PCP levels increased over time. PCP levels in human blood and urine had decreased since the 1970s, with population half-lives of 3.6 years and 5.7 years, respectively. The intervals for global population blood and urine reference values decreased to 1.1-6.3 µg/L (2002-2008) and 2.5-7 µg/L (1995-2003), respectively. The possible thyroid disrupting effects and other health risks correlated with low environmental PCP exposure should be concerning. This study can help to ascertain the effects of the banning/restriction policy, providing data for cost-benefit analysis in policy-making and further control of health risks caused by low environmental exposure to PCP.

Levels of metals and organic substances in workers at a hazardous waste incinerator: a follow-up study.

PURPOSE: To determine the blood and urine concentrations of a number of metals and organic substances in workers at a hazardous waste incinerator (HWI) in Catalonia, Spain, 8 years after regular operations in the facility. To compare these concentrations with the baseline (1999) levels and with those obtained in previous (2000 and 2005) surveys. METHODS: The employees were divided into three groups according to their specific workplaces. Plasma analyses of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs 28, 52, 101, 138, 153 and 180) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), as well as urinary analyses of 2,4- and 2,5-dichlorophenol (DCP), 2,4,5- and 2,4,6-trichlorophenol (TCP), pentachlorophenol (PCP) and 1-hydroxypyrene (1-HP) were carried out. Blood concentrations of manganese and mercury, and urinary levels of nickel were also determined. RESULTS: For organic compounds in plasma, the comparison of the current levels with those of previous surveys did not show any significant increase for any of the compounds analyzed. In contrast, plasma levels of PCBs 28, 52 and 101 were significantly lower than the respective baseline concentrations, while especially notable was the significant reduction in the levels of PCDD/Fs in plasma of plant workers, which decreased from 26.7 pg I-TEQ/g lipid in the baseline survey to the current 2.5 pg I-TEQ/g lipid. CONCLUSION: According to the results of the present study, there are no evident signs of occupational exposure to a number of metals and organic substances in the workers of the HWI.

Urinary pentachlorophenol in painters and bricklayers in a four-years time interval after the PCP prohibition ordinance in Germany.

Pentachlorophenol (PCP) was widely used as a wood preservative in Germany until 1989, when it was prohibited by law. Within a cross-sectional study we investigated the internal PCP exposure of painters and bricklayers between one year and four years after the ban. PCP was analysed in post-shift urine samples of 189 painters and 148 bricklayers by gas chromatography and electron capture detection (GC-ECD). The median PCP concentration in the urine of painters was 2.4 microg/g creatinine (range: 0.2-52 microg/g creatinine). For the bricklayers a range of 0.1-25 microg/g creatinine (median: 1.8 microg/g creatinine) was determined. The difference between both groups was statistically significant, pointing to a small additional uptake of PCP by the painters probably from an exposure to contaminated wood surfaces or residual PCP containing preservatives. The biomonitoring results for both groups coincided with background values of the general population at that time.

Twenty years of the German Environmental Survey (GerES): human biomonitoring--temporal and spatial (West Germany/East Germany) differences in population exposure.

The German Environmental Surveys (GerESs) are nationwide population studies, which have repeatedly been carried out in Germany since the mid-1980s. The subjects were representatively selected from the regional registration offices with regard to age, gender and community size. The first survey for adults (GerES I) was carried out in 1985/1986 (West Germany) followed by GerES IIa in 1990/1991 (West Germany) and GerES IIb in 1991/1992 (East Germany). In GerES II children were also included to some extent. In 1998, the third GerES for adults was conducted in both parts of Germany (GerES III). The current survey 2003/2006 (GerES IV) is focussing exclusively on children. A 1-year pilot study was conducted in 2001-2002 to collect information on parameters influencing the response rate and to test the suitability of the different instruments intended to be used for the main study. The main goal of the surveys is to analyse and document the extent, distribution and determinants of exposure to environmental pollutants of the German general population. Three main instruments of investigation were comprised in GerES: human biomonitoring (HBM), monitoring of the domestic environment, and collecting information on exposure pathways and living conditions via questionnaires. This paper is focussed on the general design of the GerESs, the trend over time and spatial differences (West Germany and East Germany) for HBM data on arsenic, cadmium, lead, mercury, pentachlorophenol (PCP), and polycyclic aromatic hydrocarbons (PAH). These substances have been determined in blood and/or morning urine of adults and children. All GerESs have been conducted in close connection with the National Health Interview and Examination Surveys performed by the Robert Koch-Institute, Berlin.

Revised reference value for pentachlorophenol in morning urine.

Reference values are continuously derived by the Human Biomonitoring Commission of the German Federal Environment Agency to give help in assessing the exposure of individuals or population groups in comparison to the background exposure. As environmental conditions may change reference values should be checked periodically and they have to be updated, if new data become available. The results of the German Environmental Survey 1998 (GerES III) showed the decreasing pentachlorophenol (PCP) exposure of the German adult population. Therefore, the reference value for PCP in morning urine was lowered: from 8 to 5 microg/l for adults (aged 18-69 years) living in homes where wood preservatives had not been used.

An observational study of the potential exposures of preschool children to pentachlorophenol, bisphenol-A, and nonylphenol at home and daycare.

The Children's Total Exposure to Persistent Pesticides and Other Persistent Organic Pollutants (CTEPP) study investigated the potential exposures of 257 preschool children, ages 1 1/2-5 yr, and their primary adult caregivers to more than 50 anthropogenic chemicals. Field sampling took place in selected counties in North Carolina (NC) and Ohio (OH) in 2000-2001. Over a 48-h period in each child's daycare center and/or home, food, beverages, indoor air, outdoor air, house dust, soil, participants' hand surfaces and urine were sampled. Additional samples-transferable residues, food preparation surface wipes, and hard floor surface wipes-were collected in the approximately 13% of the homes that had pesticide applications within the 7 days prior to field sampling. Three phenols were among the measured chemicals: pentachlorophenol (PCP), bisphenol-A [2,2-bis(4-hydroxyphenyl)propane], and nonylphenol (4-n-nonylphenol). Nonylphenol (NP) was detected in less than 11% of the samples in any medium. Among samples that were collected at all participants' homes and daycare centers, PCP was detected in >50% of indoor air, outdoor air, house dust, and urine samples; bisphenol-A (BPA) was detected in >50% of indoor air, hand wipe, solid food, and liquid food samples. The concentrations of the phenols in the sampled media were measured, and the children's potential exposures and potential absorbed doses resulting from intake through the inhalation, dietary ingestion, and indirect ingestion routes of exposure were estimated. The children's potential exposures to PCP were predominantly through inhalation: 78% in NC and 90% in OH. In contrast, their potential exposures to BPA were predominantly through dietary ingestion: 99%, for children in both states. The children's estimated exposures to PCP, calculated from the amounts excreted in their urine, exceeded their estimated maximum potential intake, calculated from the multimedia PCP concentrations, by a factor greater than 10. This inconsistency for PCP highlights the need for further research on the environmental pathways and routes of PCP exposure, investigation of possible exposures to other compounds that could be metabolized to PCP, and on the human absorption, metabolism, and excretion of this phenol over time periods longer than 48 h.

Exposure to indoor pesticides during pregnancy in a multiethnic, urban cohort.

Evidence is growing that indoor pesticide exposure is of considerable magnitude in the United States and that pesticide concentrations may be especially high in urban areas. Of particular concern is exposure of pregnant women because animal data suggest that exposure to pesticides during pregnancy and early life may impair neurodevelopment in the offspring. To investigate the relationship between prenatal exposure to indoor pesticides and infant growth and development, we are conducting a prospective, multiethnic cohort study of mothers and infants delivered at Mount Sinai Hospital in New York City. This article provides data on pesticide exposure based on questionnaire items and analysis of maternal urinary metabolite levels among 386 women. Both the questionnaire and laboratory data revealed that exposure to indoor pesticides was considerable. The proportion of women estimated from questionnaire data as having been exposed during pregnancy to indoor pesticides (approximately 70%) was somewhat lower than the 80-90% of American households who reportedly used pesticides in previous surveys, but some of the latter surveys included both indoor and outdoor pesticide use. Urinary metabolite levels of 3,5,6-trichloro-2-pyridinol (TCPy; median = 11.3 micro g/g creatinine), phenoxybenzoic acid (PBA; median =19.3 micro g/g creatinine), and pentachlorophenol (PCP; median =7.3 micro g/g creatinine) were higher than those reported in other studies of adults in the United States. Furthermore, no associations were evident between the pesticide questionnaire data and the urinary metabolites. Assessments of sociodemographic and building characteristics with questionnaire data and the metabolite levels revealed no consistent trends. Significant temporal variations were observed for urinary PBA but not TCPy or PCP. The temporal variations for PBA were consistent with seasonal spraying of pyrethroid pesticides. These data underscore the need to assess the potentially adverse effects of pesticide exposure on fetuses and infants and the importance of finding alternative methods for pest management to reduce pesticide exposures.

Predictive value of human biomonitoring in environmental medicine: experiences at the outpatient unit of environmental medicine (UEM) of the University Hospital Aachen, Germany.

There is little data on the distribution of biomonitoring parameters in patients at outpatient Units of Environmental Medicine (UEM). We evaluated the biomonitoring parameters of 646 UEM outpatients from our University Hospital 1988-1998. Few patients were exposed to specific substances. Data of patients who were not obviously exposed was analysed statistically (geometric mean, standard deviation, median, 95th percentile). Results were compared with reference values in literature. Normal distribution of biomonitoring parameters was rare. 95th percentiles for arsenic, chromium, selenium, zinc, phenol and toluene were below standard, 95th percentiles for copper and mercury above, and 95th percentiles for lead, cadmium, pentachlorophenol, lindane, and beta-hexachlorocyclohexane were within the published range of reference values. Thallium as well as most volatile organic compounds analyzed were below detection levels. Aluminum and fluorine exposure was rarely analysed. In view of these results, it is concluded that the indication for biomonitoring needs to be stringent as levels of biomonitoring parameters are generally not risen in patients of the UEM.

Biotransformation of pentachlorophenol, aniline and biphenyl in isolated rainbow trout (Oncorhynchus mykiss) hepatocytes: comparison with in vivo metabolism.

1. The biotransformation of pentachlorophenol (PCP), aniline and biphenyl in rainbow trout (Oncorhynchus mykiss) isolated liver cells was investigated to examine if fish hepatocytes represent a suitable alternative to the in vivo approach for studying the biotransformation of chemicals. Each compound was incubated at two concentrations (10 and 60 microM) for 2 h. For comparison, the metabolic profile of these xenobiotics was also studied in urine and bile of trout orally exposed to 1.8-4.0 mg/kg wet wt of each compound. 2. In vitro as in vivo, PCP glucuronide and to a lesser extent PCP sulphate were the metabolites formed by trout from PCP. 3. Aniline was mainly metabolized to acetanilide and to a lesser extent to 2-aminophenol by isolated hepatocytes, but neither hydroxylated acetanilide nor conjugates were found in vitro whereas they were present in bile and urine of trout treated with this chemical. 4. Trout hepatocytes metabolized biphenyl to hydroxylated and dihydroxylated products and the corresponding glucuronides. These results correlated well with the metabolic profile obtained from the bile of trout exposed to this pesticide. 5. It is concluded that although hepatocytes are well suited for several types of biotransformation studies, the fact that this system may in some cases produce a different metabolic pattern than in vivo should be considered when attempting to extrapolate in vitro to in vivo data.

Feeding fish oil to rats accelerates the metabolism of hexachlorobenzene.

This study was conducted to examine the influence of dietary fat on the metabolism and excretion of hexachlorobenzene (HCB), a ubiquitous food contaminant which is metabolized at a low rate. Three groups of rats were fed semi-purified diets containing 10 g/100 g of either soybean oil, lard or fish oil for 2 wk and then given a single dose of HCB by intragastric gavage. The concentrations of HCB and pentachlorophenol (PCP), a major metabolite of HCB, were monitored in the blood for 5 d. Fecal excretion of HCB did not differ among the three groups, indicating no difference in HCB retained in the body among the groups. Concentrations of HCB in blood, liver and brain samples from the lard and fish oil groups, the members of which had a low fat tissue mass, were consistently higher as compared with those in samples from the soybean oil group. The concentration of PCP and the PCP/HCB ratio in the blood were higher in the fish oil group than in the other groups. In addition, the amount of PCP excreted in urine was highest in the fish oil group. The hepatic cytochrome P-450 content in the fish oil group was higher than that in the other groups. These findings indicate that feeding fish oil to rats accelerated HCB metabolism. An increase in hepatic HCB concentration due to a small fat tissue mass and high hepatic cytochrome P-450 content may have played a role in accelerating HCB metabolism in the fish oil group.

Sensitive spectrophotometric method for determining pentachlorophenol in various environmental samples.

A new, simple, and sensitive spectrophotometric method is described for determination of pentachlorophenol, a widely used insecticide and herbicide, in various environmental samples. The method is based on the reaction of pentachlorophenol with concentrated nitric acid to form chloranil, which liberates iodine from potassium iodide. The liberated iodine then selectively oxidizes leucocrystal violet to form crystal violet, which has an absorption maximum at 592 nm. Beer's law is obeyed over the concentration range of 0.1-1.6 micrograms pentachlorophenol/25 mL (0.004-0.064 ppm). The method was applied satisfactorily to determination of pentachlorophenol in air, water, plant material, textile effluent, and biological samples.

Pentachlorophenol in the indoor environment: evidence for a correlation between pentachlorophenol in passively deposited suspended particulate and in urine of exposed persons.

Analysis of passively deposited suspended particulate (PDSP) proved to be a reliable and easily applicable method for the investigation of pentachlorophenol (PCP) exposure from indoor air. PDSP was analyzed after manual collection of samples in 78 rooms with wooden paneling, where earlier treatment with wood preservatives was suspected. Pentachlorophenol was quantitatively determined by gas chromatography with an electron capture detector following derivatization with acetic anhydride. For biological monitoring of PCP, morning urine specimens were collected from 135 persons living in the rooms investigated. After acidic hydrolysis, these samples were analyzed for PCP. The urine samples from 9% of the test-persons exceeded a PCP level of 10 micrograms/g creatinine. From this urine level, a corresponding PCP level of approximately 40 micrograms/g in PDSP could be calculated. These results show that there is still a considerable risk of exposure to PCP, even after a long period following treatment of wood with PCP-containing preservatives.

Normal values for pentachlorophenol in urine samples collected from a general population.

Aliquots of urine samples collected over a 24-h period from normal individuals were analyzed for pentachlorophenol (PCP). Urine samples were taken from subjects living in various regions (both rural and urban) throughout the province of Saskatchewan. Urinary PCP concentrations were determined with gas chromatography-mass spectrometry and stable isotope dilution. The normal PCP concentrations were found to range from 0.05 to 3.6 ng/mliters. Because the aliquots analyzed were taken from 24-h sample collections, the normal range of PCP excreted on a daily basis was determined. A total of 69 samples taken from 26 males and 43 females who ranged in age from 6 to 87 years were analyzed. The average amount of excreted PCP was determined to be 4.3 nmol/day.

Determination of pentachlorophenol in commercially prepared lyophilized human urine control samples.

Commercially available reference materials consisting of lyophilized human urine are routinely utilized by clinical chemists to monitor laboratory performance for a variety of analyses. In this study commercially prepared lyophilized human urine control samples were reconstituted and analyzed for pentachlorophenol. Based on replicate analyses of two different reference materials, the levels of PCP in each were found to be representative of the levels typically present in urine samples collected from the general population of the province of Saskatchewan.